Granted Patent B2

US 9,371,339 · App. 14/243,044 · Granted Jun 21, 2016

Abstract

Claims (50)

1. A process for the production of silahydrocarbons, comprising:

reacting at least one first reactant with at least one second reactant in the presence of a catalyst, to produce silahydrocarbons having the general formulae R 1 R 2 R 3 R 4 Si, R 1 R 2 R 3 Si(Q)SiR 1 R 2 R 3 , R 5 R 6 R 7 R 8 Si, R 5 R 6 R 7 Si(Q)SiR 5 R 7 R 8 , (R 1 ) 2 Si[QSi(R 1 ) 3 ] 2 , R 1 Si[QSi(R 1 ) 3 ] 3 , or Si[QSi(R 1 ) 3 ] 4 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are selected from the group consisting of aliphatic, aryl, alkaryl, aralkyl, and cycloaliphatic univalent hydrocarbyl groups having from one to thirty carbon atoms, with the proviso that at least one of R 5 , R 6 , R 7 , or R 8 has an alkenyl functional group; and Q is a straight or branched alkylene group having from two to twenty carbon atoms;

wherein the first reactant is selected from the group consisting of olefins of 2 to 30 carbon atoms and alkenylsilanes of general formulae (R 1 ) 2 Si(R k ) 2 (R 1 ) 3 Si(R k ), (R 1 )Si(R k ) 3 , Si(R k ) 4 or a combination of two or more thereof, wherein R k is an alkenyl group of two to thirty carbons and R 1 is an aliphatic, aryl, alkaryl, aralkyl, and cycloaliphatic univalent hydrocarbyl groups having from one to thirty carbon atoms;

wherein the second reactant is selected from the group consisting of (i) a monosilane (SiH 4 ) and hydridosilanes of general formulae, R′SiH 3 , (R′) 2 SiH 2 , or (R′) 3 SiH, or (R′) n H 3-n SiQSi(R′) y H 3-y wherein n is 0, 1, 2, or 3, y is 0, 1, 2, or 3, n+y≧1 R′ is an aliphatic, aryl, alkaryl, aralkyl, and cycloalpihatic univalent hydrocarbyl group having from one to thirty carbon atoms, or a combination of two or more thereof, or (ii) an alkenyl silane of the formula (R 1 )(R k ) 2 SiH, (R 1 ) 2 (R k )SiH, or a combination thereof, wherein R k is an alkenyl group of two to thirty carbons and R 1 is an aliphatic, aryl, alkaryl, aralkyl, and cycloaliphatic univalent hydrocarbyl groups having from one to thirty carbon atoms, or a combination of two or more thereof; and

wherein the catalyst is selected from the group consisting of an iron complex of Formula (I), an iron complex of Formula (II), or a cobalt complex of Formula (III):

wherein:

G is Fe;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 2 -R 9 , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 23 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 23 optionally contains at least one heteroatom; optionally, any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 23 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure

wherein L 1 -L 2 is

wherein each occurrence of R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, or C2-C18 alkynyl, wherein R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 , other than hydrogen, optionally contain at least one heteroatom, and R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 , other than hydrogen, are optionally substituted,

each occurrence of R 12 is independently C1-C18 alkylene, C1-C18 substituted alkylene, C2-C18 alkenylene, C2-C18 substituted alkenylene, C2-C18 alkynylene, C2-C18 substituted alkynylene, arylene, substituted arylene, wherein R 12 optionally contains at least one heteroatom;

optionally any two of R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 taken together form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 17 and R 18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R 17 and R 18 optionally contains at least one heteroatom, and wherein R 17 and R 18 taken together optionally form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 19 and R 20 is independently a covalent bond that connects Si and C, an alkylene, substituted alkylene, or a heteroatom, wherein R 19 and R 20 optionally contain at least one heteroatom;

wherein L 1 -L 2 bonds with G through unsaturated sites S 1 and S 2 ;

each occurrence of Ar is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein Ar optionally contains at least one heteroatom;

Z is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent;

R 7 , R 8 and R 9 are independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent;

X is N 2 , CO, alkyl, OH, SH, SeH, —H, or SiR 3 where R is an alkyl, aryl, or siloxanyl group;

with the provisos that

(1) R 1 in Formula (I) is hydrogen, methyl, ethyl or n-propyl;

(2) L 1 -L 2 of Formula (A) is selected from the group consisting of 1,3-divinyltetramethyldisiloxane, 1,3-butadiene, 1,5-cyclooctadienes, dicyclopentadienes, and norbornadienes;

(3) the second reactant is selected from a silane of (i) or (ii) when the catalyst is a compound of Formula (III); and

(4) the second reactant is selected from a silane of Formula (ii) when the catalyst is a compound of Formula (I) or (II).

2. The process of claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently selected from the group consisting of hydrogen, methyl, ethyl, octyl, octadecyl, phenyl, phenylethyl, and cyclohexylpropyl groups.

3. The process of claim 1 , wherein the silahydrocarbon produced by the process is selected from the group consisting of methyltri(octyl)silane, dimethyl(dioctyl)silane, methyl(hexyl)(decyl)octadecylsilane, tetra(octyl)silane, phenyltri(octyl)silane, phenyl(dipentyl)dodecylsilane, phenyl(dinonyl)butylsilane, octyltridecylsilane, octyltris(octadecyl)silane, hexyldecylbis(tetradecly)silane, phenyloctyldidecylsilane, octyldihexyloctadecylsilane, octyltriethylsilane, and/or octadecyltriethylsilane.

4. The process of claim 1 , wherein the silahydrocarbon produced by the process is selected from the group consisting of dimethyldi(decenyl)silane, dioctlyldi(tetradecenyl)silane, methyl(octyl)di-(hexenyl)silane, phenyl(nonyl)di(dodecenyl)silane, octyl(decyl)(octenyl)-(decenyl)silane, triethylocteylsilane, phenyl(heptyl)(nonenyl)(undecenyl)silane, tri(octyl)(hexadecenyl)silane, cyclohexyl(phenethyl)(heptyl)(nonenyl)silane, methyl(hexyl)(decyl)(dodecenyl)silane, ethyldi(pentyl)(tetradecenyl)silane, phenylhexylbis(2-octenyl)silane, phenyldecylbis(2-octenyl)silane, phenyloctadecylbis(2-octenyl)silane, and/or phenyoctylbis(2-octenyl)silane.

5. The process of claim 1 , wherein the silahydrocarbon produced by the process is a polysilahydrocarbon selected from the group consisting of (C 2 H 5 ) 3 Si(CH 2 ) 8 Si(C 2 H 5 ) 3 , C 6 H 5 (C 8 H 17 ) 2 Si(CH 2 ) 8 Si(C 2 H 5 ) 3 , C 6 H 5 CH 3 Si[(CH 2 ) 8 SiC 6 H 5 (CH 3 ) 2 ] 2 , C 6 H 5 Si[(CH 2 ) 8 Si(C 2 H 5 ) 3 ] 3 , C 6 H 13 Si[C 3 H 6 Si(C 4 H 9 ) 3 ] 3 , C 8 H 17 Si[C 3 H 6 Si(C 10 H 21 ) 3 ] 3 , or Si[C 2 H 4 Si(C 12 H 25 ) 3 ] 4 .

6. The process of claim 1 , wherein said first reactant is an olefin of 2 to 30 carbon atoms and said second reactant is selected from the group consisting of primary silanes of general formula, R′SiH 3 , secondary silanes of general formula, (R′) 2 SiH 2 , and tertiary silanes of general formula, (R′) 3 SiH.

7. The process of claim 1 , wherein said first reactant is an olefin of 2 to 30 carbon atoms and said second reactant is selected from the group consisting of alkylbis(alkenyl)silanes and arylbis(alkenyl)silanes of formula, R 1 (R k ) 2 SiH, and alkenylbis(alkyl)silanes and arylalkenylalkylsilanes of formula, (R 1 ) 2 R k SiH.

8. The process of claim 1 , wherein said catalyst of Formula (I) is [( 2,6-(R″)2 PDI)Fe(N 2 )] 2 (μ 2 -N 2 ), where R″ represents R 1 and/or R 2 in Formula (I).

9. The process of claim 8 , wherein R″ is independently chosen from methyl, ethyl, and mesityl.

10. The process of claim 1 , wherein the catalyst of Formula (II) is selected from the group consisting of ( 2,6-(R″)2 PDI)Fe(M vi M vi ) and ( 2,6-(R″)2 PDI)Fe(H 2 C═CHCH═CH 2 ), where R″ represents R 1 and R 2 in Formula (II).

11. The process of claim 10 , wherein R″ is independently chosen from methyl, ethyl, and mesityl.

12. The process of claim 1 , wherein the reaction temperature is 0-300° C.

13. The process of claim 1 , wherein the reaction temperature is 20-100° C.

14. The process of claim 1 , wherein the catalyst is present in an amount of from about 0.01 mole percent to about 10 mole percent based on the quantity of the olefins.

15. The process of claim 1 , wherein the catalyst is present in an amount of from about 0.1 mole percent to about 5 mole percent based on the quantity of the olefins.

16. The process of claim 1 , wherein the catalyst of Formula (III) is selected from the group consisting of ( Mes PDICoCH 3 ), ( Mes PDIMeCoCH 3 ), ( 2,6-iPr PDICoN 2 ) ( 2,6-iPr PDIMeCoN 2 ) ( 2,6-iPr PDIPhCoN 2 ), ( 2,6-iPr PDIMeCoOH), ( Mes PDI)CoOH, ( 2,6-Et PDI)CoN 2 , and ( 2,6-iPr BPDI)CoN 2 .

17. A process for hydrosilylation/dehydrogenative silylation synthesis comprising reacting C2-C30 olefins and primary silanes of general formula, R′SiH 3 or monosilane (SiH 4 ) in the presence of the catalyst of Formula (III)

wherein:

each occurrence of Ar is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein Ar optionally contains at least one heteroatom;

Z is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent;

R 7 , R 8 and R 9 are independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent;

X is N 2 , CO, alkyl, OH, SH, SeH, —H, or SiR 3 where R is an alkyl, aryl, or siloxanyl group;

to produce alkylbis(alkenyl)-silanes and arylbis(alkenyl)silanes of formula, R 1 (R k ) 2 SiH, alkenylbis(alkyl)silanes and arylalkenylalkylsilanes of formula, (R 1 ) 2 R k SiH, or tetralkenylsilanes of general formula Si(R k ) 4 , wherein R 1 is an aliphatic, aryl, alkaryl, aralkyl, and cycloaliphatic univalent hydrocarbyl groups having from one to thirty carbon atoms; R′ is an aliphatic, aryl, alkaryl, aralkyl, and cycloaliphatic univalent hydrocarbyl group having from one to thirty carbon atoms such as methyl, ethyl, octyl, octadecyl, phenyl, tolyl, phenylethyl, mesityl and cyclohexylpropyl; and R k is an alkenyl group of two to thirty carbons.

18. The process of claim 17 , wherein the catalyst of Formula (III) is selected from the group consisting of ( Mes PDICoCH 3 ), ( Mes PDIMeCoCH 3 ), ( 2,6-iPr PDICoN 2 ) ( 2,6-iPr PDIMeCoN 2 ) ( 2,6-iPr PDIPhCoN 2 ), ( 2,6-iPr PDIMeCoOH), ( Mes PDI)CoOH, ( 2,6-Et PDI)CoN 2 , and ( 2,6-iPr BPDI)CoN 2 .

19. The process of claim 17 , wherein the reaction temperature is 0-300° C.

20. The process of claim 17 , wherein the reaction temperature is 20-100° C.

Assignments (18)